Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/12—Polymerisation in non-solvents
  • C08F2/16—Aqueous medium
  • C08F2/18—Suspension polymerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate

Definitions

• the present invention relates to the sector of agents for improving the optical properties, such as in particular the opacity and / or brightness, dry products containing mineral materials containing said agents.
• R 1 and R 2 represent a linear or branched alkyl radical having a number of carbon atoms ranging from 1 to 5,
• this use in a process for the manufacture of dry products based on mineral materials is characterized in that said polymers are used as direct additives in the field of plastics, as well as in the field of aqueous formulations and especially in the paper sectors and particularly in paper coating coatings, in aqueous paint formulations and in cosmetic formulations.
• the plastics thus obtained have a high opacity and / or gloss.
• the aqueous formulations previously obtained then allow, after drying, to obtain dry products whose opacity and / or gloss is improved.
• These dry products are dry coatings which are dry films resulting from the drying of a coating color, dry films resulting from the drying of an aqueous paint formulation, or dry films resulting from the drying of an aqueous cosmetic formulation. .
• the invention relates secondly to the use of a dispersion and / or an aqueous suspension of mineral materials containing said polymers, in a process for manufacturing dry products containing mineral materials, as opacity improvers and / or the gloss of said dry products, in the fields of paper and in particular in paper coating coatings and in bulk, in aqueous paints, and in cosmetic compositions.
• Said formulations then allow, after drying, to obtain dry products whose opacity and / or gloss is improved.
• dry products are either paper loaded by the previous mass charges, or dry coatings which are dry films resulting from the drying of a coating color, dry films resulting from the drying of an aqueous formulation of paint, or dry films resulting from the drying of a cosmetic aqueous formulation.
• the dispersion and / or the aqueous suspension of mineral matter previously obtained can be dried, and the dry powders thus obtained then allow the manufacture of plastics whose opacity and / or gloss is improved.
• Said dry powders also make it possible to manufacture aqueous formulations of mineral materials, in particular paper coating coatings, mass fillers, aqueous paints and cosmetic formulations.
• dry products whose opacity and / or gloss is improved.
• dry products are either paper loaded by the previous mass charges, or dry coatings which are dry films resulting from the drying of a coating color, dry films resulting from the drying of an aqueous formulation of paint, or dry films resulting from the drying of a cosmetic aqueous formulation.
• the invention also relates to dispersions and aqueous suspensions of mineral substances, aqueous formulations of mineral materials, dry powders of mineral materials, dry products of mineral materials which cover both plastics and filled papers as well as coatings. dried according to the above methods, that is to say according to the invention.
• At least one mineral material optionally at least one dispersing agent and / or at least one grinding aid agent, and optionally at least one polymer whose use is the subject of the invention.
• aqueous formulations in question are obviously previously applied to supports; these can be as varied as the concrete, cement, plaster, wood, glass or metal as part of a painting, paper or cardboard as part of a coating sauce, or skin as part of a cosmetic formulation , without this list being exhaustive.
• the Applicant refers to the term "dry powders", the products resulting from the drying of dispersions and / or aqueous suspensions of mineral matter defined above, and which contain: at least one mineral material, - and at least one polymer whose use is the subject of the invention.
• dry products thus refers to both plastic materials and filled papers but also "dry coatings", namely, dry coatings which are dry films resulting from the drying of a coating color, dry films resulting from the drying of an aqueous paint formulation, or dry films resulting from the drying of an aqueous cosmetic formulation.
• JP 06 211 951 discloses a copolymer made from an alkyl methacrylate group having 1 to 4 carbon atoms, an alkyl methacrylate group having 6 to 30 carbon atoms. , and a polyoxyalkylene group having a polymerizable function, and used for the dispersion of pigments.
• a paint made from this copolymer and containing titanium dioxide has a high gloss.
• US 2005 0004317 teaches a composition containing organic or inorganic pigments and a mixture of a block copolymer obtained by the technique.
• ATRP ATRP and a compound of the organic acid or alkyl halide or sulfonic ester type, said compound being capable of forming a salt in water.
• Calcium carbonate is mentioned as a mineral filler, and said blends of copolymer and salt act as effective dispersants of the mineral filler in water, and improve the gloss of the final product.
• JP 57 106 797 describes an aqueous suspension of calcium carbonate treated with a copolymer of acrylic acid, with maleic or sulfonic acid or lignosulfonic or phosphoric acid. Coating sauces made from aqueous suspensions of these treated fillers make it possible to manufacture papers whose opacity, brightness and whiteness are improved.
• a first object of the invention is therefore the use in a manufacturing process of dry products based on mineral materials, as agents improving the opacity and / or brightness of said dry products, water-soluble polymers of controlled structure obtained by a controlled radical polymerization process employing, as a polymerization initiator, a particular alkoxyamine of general formula (A).
• this use of said water-soluble polymers is characterized in that the process for producing said dry products comprises at least one grinding step and / or at least one dispersion step and / or at least one concentration step in the grinding process.
• water of mineral matter which leads to the production of a dispersion and / or an aqueous suspension of mineral matter.
• the dispersion and / or the aqueous suspension of mineral matter thus obtained makes it possible to produce aqueous formulations of mineral materials, in the fields of paper and in particular in paper coating coatings and in bulk filler, in aqueous paints, and in cosmetic compositions. Said formulations then make it possible, after drying, to obtain dry products whose opacity and / or gloss is improved, dry products which are either papers loaded from the previous mass charges, or dry coatings which are films. dry films resulting from the drying of said paper coating coatings, either dry paint films resulting from the drying of said aqueous paint formulations or finally dry films resulting from the drying of said cosmetic aqueous formulations.
• the invention consists in the fact that the use in a manufacturing process of mineral-based dry products is characterized in that said polymers are used as direct additives in the field of plastics and in the field of aqueous formulations and in particular in the fields of paper and particularly in paper coating coatings, in aqueous paints and in cosmetic compositions.
• the dispersion and / or the aqueous suspension of mineral matter thus obtained makes it possible to produce aqueous formulations of mineral materials, in the fields of paper and in particular in paper coating coatings and in bulk filler, in aqueous paints, and in cosmetic compositions. Said formulations then make it possible, after drying, to obtain dry products whose opacity and / or gloss is improved, dry products which are either papers loaded from said mass loads, or dry coatings and in particular dry films. resulting from the drying of said paper coating coatings, either dry paint films resulting from the drying of said aqueous paint formulations, or finally dry films resulting from the drying of said aqueous cosmetic formulations.
• This polymerization process uses, as a polymerization initiator, a particular alkoxyamine of general formula (A):
• R 1 and R 2 represent a linear or branched alkyl radical having a number of carbon atoms ranging from 1 to 5,
• the polymers thus obtained by the said process have the advantage of not containing compounds based on copper salts, unlike the polymers obtained by ATRP and sulfur compounds, as opposed to the products obtained via the RAFT technique, while at the same time having a controllable architecture through their polymerization process.
• the first object of the invention is therefore the use, in a manufacturing process of dry products containing mineral materials, as agents improving the opacity and / or brightness of said products, of water-soluble polymers of controlled structure obtained by a process.
• controlled-polymerization polymerization process employing, as a polymerization initiator, a particular alkoxyamine of general formula (A):
• R 4 represents a linear or branched alkyl radical having a number of carbon atoms ranging from 1 to 8, and preferably a tert-butyl radical,
• R 5 represents a linear or branched alkyl radical having a number of carbon atoms ranging from 1 to 8, and preferably a tert-butyl radical
• R 6 and R 7 represent a linear or branched alkyl radical having a number carbon atoms ranging from 1 to 8, and preferably an ethyl radical.
• this use of said water-soluble polymers is characterized in that the process for producing said dry products comprises at least one grinding step and / or at least one dispersion step and / or at least one concentration step in the grinding process.
• water of mineral matter which leads to the production of a dispersion and / or an aqueous suspension of mineral matter.
• the dispersion and / or the aqueous suspension of mineral matter thus obtained makes it possible to produce aqueous formulations of mineral materials, in the fields of paper and in particular in paper coating coatings and in bulk filler, in aqueous paints, and in cosmetic compositions. Said formulations then make it possible to manufacture dry coatings whose opacity and / or gloss is improved, in the fields of paper and in particular in coated papers from previous paper coating coatings and in papers made from previous fillers. mass, in the paint films, and in the films obtained from cosmetic compositions.
• the dispersion and / or the aqueous suspension of mineral matter previously obtained can be dried; the invention thus also relates to the dry powders thus obtained.
• Said dry powders then allow the manufacture of plastics whose opacity and / or gloss is improved.
• Said dry powders also make it possible to manufacture aqueous formulations of mineral materials, in particular paper coating coatings, mass fillers, aqueous paints and cosmetic formulations. These formulations make it possible to manufacture dry products which are dry coatings whose opacity and / or gloss is improved, and in particular coated papers from said papermaking coatings and papers made from said mass fillers, paint films and films obtained from said cosmetic formulations.
• Said formulations then allow the manufacture of dry coatings whose opacity and / or gloss is improved, in the fields of paper and in particular in coated papers, in paint films, in films obtained from cosmetic compositions, while that the direct use according to the invention of said polymers in plastics leads to the production of plastics whose opacity and / or gloss is improved.
• water-soluble polymers are also characterized in that the polymers are obtained by a controlled radical polymerization process, involving the particular alkoxyamine previously described, of monomers chosen from:
• ionic monomer which is either: i) anionic and carboxylic or dicarboxylic or phosphoric or phosphonic or sulfonic or their mixture, or ii) cationic, or iii) the mixture of i) and ii)
• n and p represent a number of alkylene oxide units of less than or equal to 150
• n represents a number of ethylene oxide units of less than or equal to 150
• q represents an integer at least equal to 1 and such that ⁇ (m + n + p) q ⁇ 150, and preferentially such that ⁇ (m + n + p) q ⁇ 120
• R 1 represents hydrogen or the methyl or ethyl radical
• - R 2 represents the hydrogen or the methyl or ethyl radical
• R ' represents hydrogen or a hydrocarbon radical having 1 to 40 carbon atoms, and preferably represents a hydrocarbon radical having 1 to 12 carbon atoms and very preferably a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several monomers of formula (I),
• water-soluble polymers are also characterized in that the water-soluble polymers are obtained by the controlled radical polymerization of monomers chosen from:
• ethylenically unsaturated anionic and monocarboxylic function in the acid or salified state chosen from monomers with ethylenic unsaturation and monocarboxylic function such as acrylic or methacrylic acid or else semiesters of diacids such as monoesters Ci-C 4 maleic or itaconic acids, or selected from the monomers with ethylenic unsaturation and dicarboxylic function in the acid or salified state such as crotonic acid, isocrotonic, cinnamic, itaconic, maleic, or the anhydrides of carboxylic acids, such as maleic anhydride or chosen from ethylenically unsaturated monomers with a sulphonic function in the acidic or salified state, such as 2-acrylamido-2-methylpropanesulphonic acid, sodium methallylsulphonate and vinylic acid.
• monomers with ethylenic unsaturation and monocarboxylic function such as acrylic or methacrylic acid
• n and p represent a number of alkylene oxide units of less than or equal to 150, n represents a number of ethylene oxide units less than or equal to
• q represents an integer at least equal to 1 and such that 5 ⁇ (m + n + p) q ⁇
• R 1 represents hydrogen or the methyl or ethyl radical
• R 2 represents hydrogen or the methyl or ethyl radical
• R represents a radical containing a polymerizable unsaturated functional group belonging to the vinyl group as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters and also to the group of urethane unsaturates such as, for example, acrylurethane, methacrylurethane, ⁇ - ⁇ '-dimethylisopropenylbenzylurethane, allylurethane, as well as the group of substituted or unsubstituted allylic or vinyl ethers, or else the group of ethylenically unsaturated amides or imides
• R ' represents hydrogen or a hydrocarbon radical having 1 to 40 carbon atoms, and preferably represents a hydrocarbon radical having 1 to 12 carbon atoms and very preferably a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several monomers of formula (I),
• At least one monomer of the acrylamide or methacrylamide type and their mixtures or else at least one non-water-soluble monomer such as alkyl acrylates or methacrylates, vinyls such as vinyl acetate, vinylpyrrolidone, styrene, Palphamethylstyrene and their derivatives, or at least one organofluorinated or organosilicinated monomer preferably chosen from the molecules of formulas (IIa) or (IIb):
• - mi, pi, ni 2 and p 2 represent a number of alkylene oxide units less than or equal to 150
• n 2 represent a number of units of ethylene oxide less than or equal to 150
• q t and q 2 represent an integer at least equal to 1 and such that 0 ⁇ (mi + ni + pi) qi ⁇ 150 and 0 ⁇ (m 2 + n 2 + p 2) q 2 ⁇ 150,
• r represents a number such that 1 ⁇ r ⁇ 200
• R 3 represents a radical containing a polymerizable unsaturated functional group belonging to the vinyl group as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters and also to the group of urethane unsaturates such as, for example, acrylurethanes, methacrylurethane, ⁇ - ⁇ -dimethylisopropenylbenzylurethane, allylurethane, as well as the group of substituted or unsubstituted allylic or vinyl ethers, or still to the group of amides or ethylenically unsaturated imides,
• R 4 , R 5 , Rio and RH represent hydrogen or the methyl or ethyl radical
• R 6 , R 7 , R 8 and R 9 represent linear or branched alkyl or aryl or alkylaryl or arylalkyl groups having 1 to 20 carbon atoms, or a mixture thereof,
• R represents a radical containing a polymerizable unsaturated functional group, belonging to the group of vinyls as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters, and also to the group of urethane unsaturates such as, for example, acrylurethanes and methacrylurethanes; ⁇ - ⁇ '-dimethyl-isopropenyl-benzylurethane, allyl urethane, as well as the group of substituted or unsubstituted allylic or vinyl ethers, or else the group of ethylenically unsaturated amides or imides,
• n 3 and U 4 represent a number of ethylene oxide units less than or equal to
• 150, q 3 and q 4 represent an integer at least equal to 1 and such that 0 ⁇ (m 3 + n 3 + p 3 ) q 3 ⁇ 150 and 0 ⁇ (m 4 + n 4 + p 4 ) q 4 ⁇ 150, r 'represents a number such that 1 ⁇ r' ⁇ 200,
• R 1 , R 5 , R 20 and R 2 1 represent hydrogen or the methyl or ethyl radical
• - R 1 O , R 7 , Ris and R 19 represent linear or branched alkyl or aryl or alkylaryl groups , or arylalkyl having 1 to 20 carbon atoms, or mixtures thereof
• D and E are optionally present groups, which then represent a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several of these monomers.
• water-soluble polymers are characterized in that said abovementioned polymers are constituted, expressed by weight, relative to the total weight of the monomers involved: from 2% to 98% and even more particularly from 5% to 95% of at least one ionic monomer which is either:
• an ethylenically unsaturated anionic monomer with a monocarboxylic functional group in the acid or salified state chosen from monomers containing ethylenic unsaturation and monocarboxylic functional groups such as acrylic or methacrylic acid or else semiesters of diacids such as C monoesters;
• n and p represent a number of alkylene oxide units of less than or equal to 150
• n a number of ethylene oxide units less than or equal to 150
• q represents an integer at least equal to 1 and such that 5 ⁇ (m + n + p) q ⁇
• R 1 represents hydrogen or the methyl or ethyl radical
• R 2 represents hydrogen or the methyl or ethyl radical
• R represents a radical containing a polymerizable unsaturated group belonging to the vinyl group as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters and also to the group of urethane unsaturates such as, for example, acrylurethane, methacrylurethane, ⁇ - ⁇ -dimethyl isopropenylbenzylurethane, allylurethane, as well as the group of substituted or unsubstituted allylic or vinyl ethers, or else the group of amides or ethylenically unsaturated imides,
• R ' represents hydrogen or a hydrocarbon radical having 1 to 40 carbon atoms, and preferably represents a hydrocarbon radical having 1 to 12 carbon atoms and very preferably a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several monomers of formula (I),
• mi, pi, m 2 and p 2 represent a number of alkylene oxide units of less than or equal to 150, ni and ⁇ . 2 represent a number of ethylene oxide units less than or equal to 150, qi and q 2 represent an integer at least equal to 1 and such that 0 ⁇
• R 3 represents a radical containing a polymerizable unsaturated functional group belonging to the vinyl group as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters and also to the group of urethane unsaturates such as, for example, acrylurethanes and methacrylurethanes.
• urethane unsaturates such as, for example, acrylurethanes and methacrylurethanes.
• R 4 , R 5 , Rio and Ri i represent hydrogen or the methyl or ethyl radical
• R 6 , R 7 , R 8 and R 8 represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having 1 to 20 carbon atoms, or their mixture,
• R represents a radical containing a polymerizable unsaturated functional group, belonging to the vinyl group as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters, as well as to the group of unsaturated urethanes such as, for example, acrylurethanes, methacrylurethanes, ⁇ - ⁇ '-dimethylisopropenylbenzylurethane, allylurethane, as well as the group of substituted or unsubstituted allylic or vinyl ethers, or else the group of ethylenically unsaturated amides or imides,
• A is a group optionally present, which then represents a hydrocarbon radical having 1 to 4 carbon atoms
• B represents a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several of these monomers
• crosslinking monomer selected from the group consisting of ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, allyl acrylate, allyl maleates, methylenebisacrylamide, methylene -bis-methacrylamide, tetralyloxyethane, triallyl cyanurates, allyl ethers obtained from polyols such as pentaerythritol, sorbitol, sucrose or the like, or chosen from the molecules of formula (III):
• r ' represents a number such that 1 ⁇ r' ⁇ 200
• - Ri 3 represents a radical containing a polymerizable unsaturated functional group, belonging to the vinyl group as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters, and also to the group of unsaturated urethanes such as, for example, acrylurethane, methacrylurethane, ⁇ - ⁇ 'dimethyl-isopropenylbenzylurethane, allylurethane, as well as the group of substituted or unsubstituted allylic or vinyl ethers, or else the group of ethylenically unsaturated amides or imides,
• R H, R 5, R 2 o and R 2] represent hydrogen or the methyl or ethyl radical
• - R 6, R] 7, R 8 and R 19 represent linear or branched alkyl groups, or aryl, or alkylaryl, or arylalkyl having 1 to 20 carbon atoms, or a mixture thereof,
• D and E are optionally present groups, which then represent a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several of these monomers.
• This use according to the invention of water-soluble polymers is also characterized in that said polymers are obtained in acid form and optionally distilled, and may also be partially or completely neutralized by one or more agents such as oxides or hydroxides of metals such as by aluminum, and in particular oxides or hydroxides of alkali metals, such as, for example, sodium, potassium, lithium, or oxides or hydroxides of alkaline earth metals such as for example calcium, magnesium, barium, or the oxides and hydroxides of transition metals such as, for example, zinc, copper, iron, or else ammonia or primary, secondary or tertiary aliphatic and / or cyclic amines such as, for example, stearylamine, ethanolamines (mono- , di-, triethanolamine), mono and diethylamine, cyclohexylamine, methylcyclohexylamine, amino methylpropanol, morpholine.
• agents such as oxides or hydroxides of metals such as by
• said polymers may optionally, before or after the total or partial neutralization reaction, be treated and separated into several phases, according to static or dynamic processes known to those skilled in the art, by one or more polar solvents belonging in particular to to the group consisting of water, methanol, ethanol, propanol, isopropanol, butanols, acetone, tetrahydrofuran or mixtures thereof.
• polar solvents belonging in particular to to the group consisting of water, methanol, ethanol, propanol, isopropanol, butanols, acetone, tetrahydrofuran or mixtures thereof.
• said polymers may optionally be dried by one of the techniques well known to those skilled in the art.
• water-soluble polymers are water-soluble copolymers and have a structure of statistical type, block, comb, grafted, or alternating.
• the liquid phase of elution is an aqueous phase.
• the mineral materials are chosen from a pigment and / or a mineral filler, selected from natural or synthetic calcium carbonate, dolomites, kaolin, talc, cement, gypsum, lime , magnesia, titanium dioxide, satin white, aluminum trioxide or aluminum trihydroxide, silicas, mica and the mixture of these fillers with each other, such as talc-calcium carbonate, carbonate mixtures calcium-kaolin, or mixtures of calcium carbonate with aluminum trihydroxide or aluminum trioxide, or mixtures with synthetic or natural fibers or the co-structures of minerals such as talc co-structures calcium carbonate or talc-titanium dioxide, or mixtures thereof.
• a mineral filler selected from natural or synthetic calcium carbonate, dolomites, kaolin, talc, cement, gypsum, lime , magnesia, titanium dioxide, satin white, aluminum trioxide or aluminum trihydroxide, silicas, mica and the mixture of these fillers with each other, such as tal
• dry powders can be dried, and the dry powders thus obtained then allow the manufacture of plastics whose opacity and / or gloss is improved.
• Said dry powders also make it possible to manufacture aqueous formulations of mineral materials, in particular paper coating coatings, mass fillers, aqueous paints and cosmetic formulations.
• Said formulations then make it possible, after drying, to obtain dry products whose opacity and / or gloss is improved, dry products which are either papers loaded from said mass loads, or dry coatings which are dry films. resulting from the drying of said paper coating coatings, either dry films resulting from the drying of said aqueous paint formulations, or finally dry films resulting from the drying of said aqueous cometic formulations.
• nonionic monomer consisting of at least one monomer of formula (I):
• n and p represent a number of alkylene oxide units of less than or equal to 150; n represents a number of ethylene oxide units of less than or equal to
• R represents a radical containing a polymerizable unsaturated functional group belonging to the vinyl group as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters and also to the group of urethane unsaturates such as, for example, acrylurethane, methacrylurethane, ⁇ - ⁇ 'dimethyl-isopropenylbenzylurethane, allyl urethane, as well as the group of substituted or unsubstituted allylic or vinyl ethers, or alternatively to the group of ethylenically unsaturated amides or imides
• R' represents hydrogen or a hydrocarbon radical having 1 to 40 carbon atoms, and preferably represents a hydrocarbon radical having 1 to 12 carbon atoms and very preferably a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several monomers of formula (I),
• m and p represent a number of alkylene oxide units of less than or equal to 150
• n represents a number of ethylene oxide units of less than or equal to 150
• q represents an integer at least equal to 1 and such that ⁇ (m + n + ⁇ ) q ⁇ 150, and preferentially such that ⁇ (m + n + p) q ⁇ 120
• R 1 represents hydrogen or the methyl or ethyl radical
• R 2 represents hydrogen or the methyl or ethyl radical
• R represents a radical containing a polymerizable unsaturated functional group, belonging to the vinyl group as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic, vinylphthalic esters as well as to the group of unsaturated urethanes such as by examples are acrylurethane, methacrylurethane, ⁇ - ⁇ -dimethylisopropenylbenzylurethane, allylurethane, as well as the group
• R ' represents hydrogen or a hydrocarbon radical having 1 to 40 carbon atoms, and preferably represents a hydrocarbon radical having 1 to 12 carbon atoms and very preferably a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several monomers of formula (I), 6 001064
• the ammethylstyrene and their derivatives, or at least one organofluorinated or organosilane monomer preferably chosen from the molecules of formulas (IIa) or (IIb):
• mi, pi, m 2 and p 2 represent a number of alkylene oxide units of less than or equal to 150
• n 2 represents a number of ethylene oxide units of less than or equal to 150
• qi and q 2 represents an integer at least equal to 1 and such that 0 ⁇ (mi + m + pi) qi ⁇ 150 and 0 ⁇ (m 2 + n 2 + p 2 ) q 2 ⁇ 150
• r represents a number such that 1 ⁇ r ⁇ 200
• R 3 represents a radical containing a polymerizable unsaturated functional group belonging to the vinyl group as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters as well as to the group of urethane unsaturates such as, for example, acrylurethanes and methacrylurethanes.
• urethane unsaturates such as, for example, acrylurethanes and methacrylurethanes.
• R 4 , R 5 , Rio and Rn represent hydrogen or the methyl or ethyl radical
• R 6 , R 7 , R 8 and R 9 represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having 1 to 20 carbon atoms, or their mixed,
• Ri 2 represents a hydrocarbon radical having 1 to 40 carbon atoms
• - A and B are optionally present groups, which then represent a hydrocarbon radical having 1 to 4 carbon atoms,
• R represents a radical containing a polymerizable unsaturated functional group, belonging to the group of vinyls as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters, and also to the group of urethane unsaturates such as, for example, acrylurethanes and methacrylurethanes; , ⁇ - ⁇ 'dimethyl-isopropenylbenzylurethane, allylurethane, as well as the group of substituted or unsubstituted allylic or vinyl ethers, or alternatively to the group of ethylenically unsaturated amides or imides, - A is an optionally present group, which represents then a hydrocarbon radical having 1 to 4 carbon atoms, B represents a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several of these monomers,
• crosslinking monomer selected from the group consisting of ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, allyl acrylate, allyl maleates, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetrallyloxyethane, triallyl cyanurates, allyl ethers obtained from polyols such as pentaerythritol, sorbitol, sucrose or the like, or chosen from the molecules of formula (III):
• p 3 , In 4 and p 4 represent a number of alkylene oxide units less than or equal to 150
• n 3 and n ⁇ represent a number of ethylene oxide units less than or equal to 150
• q 3 and q 4 represent an integer at least equal to 1 and such that 0 ⁇ (m 3 + n 3 + p 3 ) q 3 ⁇ 150 and 0 ⁇ (m 4 + n 4 + p 4 ) q 4 ⁇ 150
• R 1 represents a radical containing a polymerizable unsaturated functional group belonging to the vinyl group as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters as well as to the group of unsaturated urethanes such as, for example, acrylurethanes and methacrylurethanes; ⁇ - ⁇ '-dimethyl-isopropenylbenzylurethane, allylurethane, as well as the group of substituted or unsubstituted allylic or vinyl ethers, or else the group of ethylenically unsaturated amides or imides,
• R 14 , Ri 5 , R 20 and R 2 i represent hydrogen or the methyl or ethyl radical
• R 16 , R 17 , Ris and R 9 represent linear or branched alkyl, or aryl, or alkylaryl or arylalkyl groups having 1 to 20 carbon atoms, or their mixture,
• D and E are optionally present groups, which then represent a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several of these monomers.
• ionic monomer which is either: i) an ethylenically unsaturated anionic monomer and a monocarboxylic functional group in the acidic or salified state chosen from monomers with ethylenic unsaturation and with a monocarboxylic function such as acrylic or methacrylic acid or else semiesters of diacids, such as the C 1 -C 4 monoesters of maleic or itaconic acids, or chosen from monomers containing ethylenic unsaturation and dicarboxylic the acidic or salified state, such as crotonic acid, isocrotonic acid, cinnamic acid, itaconic acid, maleic acid, or anhydrides of carboxylic acids, such as maleic anhydride or chosen from ethylenically unsaturated monomers with a sulfonic function at acidic or salified state such as 2-acrylamido-2-methyl
• q represents an integer at least equal to 1 and such that 5 ⁇ (m + n + p) q ⁇
• R 1 represents hydrogen or the methyl or ethyl radical
• R 2 represents hydrogen or the methyl or ethyl radical
• R ' represents hydrogen or a hydrocarbon radical having 1 to 40 carbon atoms, and preferably represents a hydrocarbon radical having 1 to 12 carbon atoms and very preferably a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several monomers of formula (I),
• mi, pi, m 2 and p 2 represent a number of alkylene oxide units of less than or equal to 150
• n 1 and n 2 represent a number of ethylene oxide units of less than or equal to 150
• q i and q 2 represent an integer at least equal to 1 and such that 0 ⁇
• R 2 represents a hydrocarbon radical having 1 to 40 carbon atoms
• a and B are optionally present groups, which then represent a hydrocarbon radical having 1 to 4 carbon atoms
• R represents a radical containing a polymerizable unsaturated functional group belonging to the vinyl group as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters and also to the group of urethane unsaturates such as, for example, acrylurethane, methacrylurethane, ⁇ - ⁇ 'dimethyl-isopropenylbenzylurethane, allylurethane, as well as the group of substituted or unsubstituted allylic or vinyl ethers, or alternatively to the group of amides or ethylenically unsaturated imides, - A is a group optionally present, which then represents a hydrocarbon radical having 1 to 4 carbon atoms, B represents a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several of these monomers,
• m 3 , p 3 , Hi 4 and p 4 represent a number of alkylene oxide units of less than or equal to 150
• n 3 and ru represent a number of ethylene oxide units of less than or equal to 150
• q 3 and q 4 represent an integer at least equal to 1 and such that O ⁇ (m 3 + n 3 + p 3 ) q 3 ⁇ 150 and O ⁇ (m 4 + n 4 + p 4 ) q 4 ⁇ 150
• r ' represents a number such that 1 ⁇ r' ⁇ 200
• R 13 represents a radical containing a polymerizable unsaturated functional group belonging to the vinyl group as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters and also to the group of urethane unsaturates such as, for example, acrylurethanes and methacrylurethanes.
• urethane unsaturates such as, for example, acrylurethanes and methacrylurethanes.
• R 16 , R 17 , R 18 and R 19 represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having 1 to 20 carbon atoms, or their mixture,
• D and E are optionally present groups, which then represent a hydrocarbon radical having 1 to 4 carbon atoms, or a mixture of several of these monomers.
• This use according to the invention of a dispersion and / or a suspension containing said water-soluble polymers is also characterized in that said polymers are obtained in acid form and optionally distilled, and may also be partially or completely neutralized by one or more agents such as oxides or hydroxides of metals such as, for example, aluminum, and in particular alkali metal oxides or hydroxides, such as, for example, sodium, potassium or lithium, or oxides or hydroxides of alkaline earth metals such as that for example calcium, magnesium, barium, or the oxides and hydroxides of transition metals such as for example zinc, copper, iron, or by ammonia or aliphatic primary, secondary or tertiary amines and / or cyclic such as, for example, stearylamine, ethanolamines (mono-, di-, triethanolamine), mono and dieth
• said polymers may optionally be dried by one of the techniques well known to those skilled in the art.
• This use according to the invention of a dispersion and / or a suspension containing said water-soluble polymers is also characterized in that said polymers are water-soluble copolymers and have a structure of statistical, block, comb, grafted or alternating type .
• This molecular weight is determined according to the GPC (Gel Permeability Chromatography Chromatography) method using a Waters TM brand liquid chromatography apparatus with two detectors, one of which combines the dynamic scattering of light with the measured viscometry. by a Viscotek TM viscometer and the other being a Waters TM brand refractometric concentration detector.
• GPC Gel Permeability Chromatography Chromatography
• the liquid phase of elution is an aqueous phase.
• the mineral materials are chosen from a pigment and / or a mineral filler, selected from natural or synthetic calcium carbonate, dolomites, kaolin, talc, cement, gypsum, lime , magnesia, titanium dioxide, satin white, aluminum trioxide or aluminum trihydroxide, silicas, mica and the mixture of these fillers with each other, such as talc-calcium carbonate, carbonate mixtures calcium-kaolin, or mixtures of calcium carbonate with aluminum trihydroxide or aluminum trioxide, or mixtures with synthetic or natural fibers or the co-structures of minerals such as talc co-structures calcium carbonate or talc-titanium dioxide, or mixtures thereof.
• a mineral filler selected from natural or synthetic calcium carbonate, dolomites, kaolin, talc, cement, gypsum, lime , magnesia, titanium dioxide, satin white, aluminum trioxide or aluminum trihydroxide, silicas, mica and the mixture of these fillers with each other, such as tal
• this use is characterized in that said mineral materials are natural or synthetic calcium carbonate and more particularly a natural calcium carbonate selected from marble, calcite, chalk or mixtures thereof.
• Another subject of the invention concerns aqueous dispersions and / or suspensions of mineral matter, characterized in that they contain:
• dispersions and / or suspensions are also characterized in that they contain from 0.05% to 5%, and preferably from 0.1% to 3% by dry weight of at least one water-soluble polymer obtained by a polymerization process.
• controlled radical comprising an alkoxyamine of formula (A), based on the dry weight of mineral matter.
• aqueous formulations and in particular paper coating coatings, mass fillers, aqueous paints and cosmetic formulations, characterized in that they contain:
• At least one water-soluble polymer obtained by a controlled radical polymerization process involving an alkoxyamine of formula (A), and optionally at least one dispersing agent and / or at least one grinding aid agent different from the abovementioned polymer, and in that they are obtained by the process according to the invention.
• At least one mineral material and at least one water-soluble polymer obtained by a controlled radical polymerization process involving an alkoxyamine of formula (A).
• dry powders are also characterized in that they contain from 0.05% to 5% and preferably from 0.1% to 3% by weight of at least one water-soluble polymer obtained by a controlled radical polymerization process involving an alkoxyamine of formula (A), relative to the total weight of the powder.
• a final subject of the invention relates to the films resulting from the drying of a papermaking coating, the films resulting from the drying of an aqueous paint formulation, the films resulting from the drying of an aqueous cosmetic formulation, as well as the plastics and the loaded papers, characterized in that they contain:
• At least one mineral material and at least one water-soluble polymer obtained by a controlled radical polymerization process involving an alkoxyamine of formula (A).
• Water-soluble polymers of controlled structure are thus obtained, whose monomeric composition as well as the molecular weight (measured according to the method previously described and expressed in g / mole) are given in Tests Nos. 1 to 12.
• Test No. 6 This test results in obtaining, from a controlled radical polymerization process using, as polymerization initiator, the alkoxyamine of formula (A '), of a water-soluble polymer of composition by weight of, based on to the total mass of the monomers involved: 18.5% methacrylic acid,
• the method of manufacturing said dry products is characterized in that it comprises a step of grinding in water without grinding aid agent and a concentration step with use of said polymers, leading to the obtaining of an aqueous dispersion of mineral materials containing said polymers.
• Said dispersion makes it possible to formulate paper coating sauces which lead, after drying, to obtaining dry coatings whose opacity and gloss are improved.
• the dry extract of the suspension of mineral matter thus obtained is then equal to 20% (by dry weight of mineral matter relative to the total dry weight of the suspension).
• a dispersion of mineral matter is then obtained, the dry extract, denoted ES, is measured and expressed as a percentage by dry weight of mineral matter relative to the total weight of the suspension, the particle size characteristics thereof as determined above. ,% ⁇ 2 ⁇ m and% ⁇ l ⁇ m, remaining unchanged.
• the dispersion thus obtained is then mixed with a styrene-acrylic binder sold under the name Acronal TM S360D by BASF TM, in a proportion of 100 grams by dry weight of calcium carbonate, for 12 parts in the binder state.
• the paper coating sauces are then used to lay sheets of paper.
• Each sheet of paper, before being coated, is subjected to a light radiation of 457 nm on a black plate using an Elrepho TM 3000 spectrophotometer from Datacolor TM (Switzerland) to determine the Reflectance R b of uncoated paper on a black background.
• a polypropylene-based plastic paper marketed under the name Synteape TM by the company ARJO-WIGGINS TM is then coated by means of a laboratory coater of the type Hand Coater TM model KC202 and this, in order to obtain different weight of layer between 5 and 50 m 2 / g.
• the samples are dried at 90 ° C for 10 minutes in an oven.
• This light scattering coefficient S is plotted as a function of the layer weight and the value S for a layer weight of 20 g / m 2 is determined by interpolation.
• the different samples are then calendered at 90 ° C. and at a pressure of 60 bars, using a calender machine of the RK 22 HU type marketed by DR DRAMISCH TM & CO.
• This test illustrates the prior art and uses 1.50% by dry weight of a copolymer of the prior art comprising 70% by weight of acrylic acid and 30% by weight of anhydride. maleic, relative to the dry weight of mineral material, during the process of concentration of said mineral material.
• Test No. 14 This test illustrates the invention and implements 1.00% by dry weight of the polymer according to Test No. 11 relative to the dry weight of mineral material, during the process of concentration of said mineral material.
• Test No. 15 This test illustrates the invention and implements 1.20% by dry weight of the polymer according to Test No. 11 with respect to the dry weight of mineral material, during the process of concentration of said mineral material.
• Table 1 characteristics of aqueous dispersions of mineral matter and optical properties of dry coatings.
• Table 1 demonstrates that the characteristics of the aqueous dispersions according to the invention are similar to those of the dispersion according to the prior art, in terms of dry extract and granulometry.
• This example illustrates the use according to the invention of water-soluble polymers of controlled structure obtained by a controlled radical polymerization process implementing, as a polymerization initiator, a particular alkoxyamine of formula (A '), as well as the use according to the invention of aqueous dispersions of mineral materials containing said polymers, in a process for the manufacture of dry products containing mineral materials, as agents improving the opacity and brightness of said dry products.
• the method of manufacturing said dry products is characterized in that it comprises a step of grinding in water and a step of concentration in water of said mineral materials: the two stages take place with the use of polymers according to the invention or according to the prior art. It leads to obtaining an aqueous dispersion of mineral materials containing said polymers, which make it possible to manufacture coating colors.
• the manufacturing process is also characterized in that it makes it possible to obtain dry coatings, resulting from the drying of said coating coatings previously applied to papers.
• the first step is wet grinding, according to the methods well known to those skilled in the art, a calcium carbonate marketed by OMY A TM under the name Omyacarb TM 10 AV and this by using a polymer of the prior art or a polymer according to the invention.
• the percentage by weight of particles having a diameter of less than 1 ⁇ m and 2 ⁇ m is then determined using a Sedigraph TM 5100 device marketed by MICROMERITICS TM, denoted% ⁇ 1 ⁇ m and% ⁇ 2 ⁇ m.
• the suspension obtained is then concentrated in the presence of a dispersant of the prior art or by use of a polymer according to the invention: it is the same polymer as that used during the grinding step.
• a dispersion of mineral matter is then obtained, the dry extract of which is noted as ES 2 (in% by dry weight of mineral matter relative to the total dry weight of the suspension), the granulometric characteristics thereof as determined above. remaining unchanged.
• the dispersion thus obtained is then mixed with a styrene-acrylic binder sold under the name Acronal TM S360D by BASF TM, in a proportion of 100 grams by dry weight of calcium carbonate, for 12 parts in the binder state.
• a polypropylene-based plastic paper marketed under the name Synteape TM by the company ARJO-WIGGINS TM is then coated by means of a laboratory coater of the type Hand Coater TM model KC202 and this, for obtain different layer weights between 5 and 50 g / m 2 .
• the samples are dried at 90 ° C. for 10 minutes in an oven.
• This test illustrates the prior art and uses 0.25% by dry weight, relative to the dry weight of mineral matter, of a copolymer composed of 70% of acrylic acid and 30% of maleic anhydride (in % by weight of monomers), during the grinding, and 0.45% by dry weight of the same copolymer relative to the dry weight of mineral material during the concentration step.
• Test No. 18 This test illustrates the invention and uses 0.25% by dry weight of the polymer according to Test No. 3 with respect to the dry weight of mineral material, during the milling stage, and 0.45% by weight. % by dry weight of the same copolymer relative to the dry weight of mineral material during the concentration step.
• This test illustrates the invention and uses 0.25% by dry weight of the polymer according to test No. 2 relative to the dry weight of mineral material, during the grinding stage, and 0.45% by dry weight. of the same copolymer relative to the dry weight of mineral material during the concentration step.
• This test illustrates the invention and uses 0.15% by dry weight of the polymer according to test No. 3 relative to the dry weight of mineral material, during the grinding stage, and 0.45% by dry weight. of the same copolymer relative to the dry weight of mineral material during the concentration step.
• Table 2 demonstrates that the characteristics of the aqueous dispersions according to the invention are similar to those of the dispersion according to the prior art, in terms of dry extract ES 2 and particle size.
• the opacity in terms of measurement of the light scattering coefficient S, and the gloss, in terms of the measurement of the coefficient B 75 , of the dry films resulting from the drying of the coating colors containing said dispersions, is greater in the frame of the method according to the invention.
• This example illustrates the use according to the invention of water-soluble polymers of controlled structure obtained by a controlled radical polymerization process implementing, as a polymerization initiator, a particular alkoxyamine of formula (A '), as well as the use of aqueous suspensions containing said polymers, in a process for the manufacture of dry products containing inorganic materials, as improving agents the brightness and whiteness of said dry products.
• the method of manufacturing said dry products is characterized in that it comprises a step of grinding in the water of the mineral materials using a polymer of the prior art or using polymers according to the invention , leading to the production of an aqueous suspension of mineral matter. This suspension makes it possible to manufacture a coating color.
• the manufacturing process is also characterized in that it applies to the manufacture of dry coatings which are dry films resulting from the drying of said coating coatings which have been previously applied to papers, which are coated papers from papermaking coating sauces containing said suspensions.
• wet grinding is firstly carried out according to the methods well known to those skilled in the art, a calcium carbonate which is a calcite originating from Orgon (France), using a polymer of the prior art or by use of a polymer according to the invention.
• the dry extract is then determined as a percentage by dry weight of mineral matter relative to the total dry weight of the suspension, and the percentage by weight of particles whose diameter is less than 1 ⁇ m, denoted% ⁇ 1 ⁇ m, using a Sedigraph TM 5100 device marketed by MICROMERITICS TM.
• a paper coating sauce is then produced containing:
• Mowiol TM 6.98 which is a polyvinyl alcohol marketed by CLARIANT TM
• DL966 which is a latex marketed by DOW TM
• the pH of the sauce is fixed at 8.5 by adding sodium hydroxide.
• a pre-coated backing paper whose weight is equal to 76 g / m 2 is then coated by means of a laboratory coater of the type Hand Coater TM model KC202, in order to obtain an equal layer weight. at 10 g / m 2 .
• the samples are then dried for 10 minutes in an oven at 90 ° C.
• the coated paper is then calendered at 80 ° C. and at a pressure of 40 bars, using a calender machine of the RK 22 HU type marketed by the company DR DRAMISCH TM & CO.
• B 75 a measurement of the 75 ° TAPPI brightness, denoted B 75 , according to the TAPPI T480 os-78 standard, is carried out using a laboratory glossmeter of the LGDL-05/2 type. marketed by LEHMANN MESSTECHNIK TM.
• WQ E whiteness measurement
• This test illustrates the prior art and implements 1.35% by weight, relative to the dry weight of mineral matter, of a polymer of the prior art which is a homopolymer of acrylic acid neutralized with a mixture of 50% sodium hydroxide and 50% magnesium hydroxide (in molar equivalent), during the grinding step.
• This test illustrates the prior art and uses, during the grinding stage, 1.35% by weight, relative to the dry weight of mineral matter, of a polymer of the prior art which is obtained by radical polymerization. Conventional and which is composed, in percentage by weight, of 81.5% of methoxy polyethylene glycol methacrylate of molecular weight 2000, 4.9% of methacrylic acid, and 13.6% of acrylic acid.
• Test No. 23 This test illustrates the invention and implements 1.35% by weight, relative to the dry weight of mineral matter, of a polymer according to test No. 1, during the grinding step .
• Table 3 characteristics of aqueous suspensions of mineral matter and optical properties of dry coatings.
• This example illustrates the use according to the invention of water-soluble polymers of controlled structure obtained by a controlled radical polymerization process employing, as a polymerization initiator, a particular alkoxyamine of general formula (A '), as well as use of the aqueous suspensions containing said polymers, in a process for the manufacture of dry products containing inorganic materials, as agents improving the opacity of said dry products.
• the manufacturing process of said dry products is characterized in that it comprises a step of grinding in the water of the mineral materials using a polymer of the prior art or using polymers according to the invention, leading to the production of an aqueous suspension of mineral matter.
• This suspension makes it possible to manufacture a coating color.
• the manufacturing process is also characterized in that it makes it possible to obtain dry coatings which are dry films resulting from the drying of said coating coatings which have previously been applied to papers.
• Coated papers are produced according to the same method as that described for Example 2.
• the value of the diffusion coefficient of the light S (m 2 / kg) is then determined before calendering, according to the same method as that described in Example 2.
• This test illustrates the prior art and implements 1.35% by weight, relative to the dry weight of mineral matter, of a polymer of the prior art which is a homopolymer of acrylic acid neutralized with a mixture of 50% sodium hydroxide and 50% magnesium hydroxide (in molar equivalent), during the grinding step.
• This test differs from Test No. 21 in that the grinding operation was stopped so as to obtain a dry extract equal to 73.2% by dry weight of mineral matter relative to the total dry weight of the suspension. .
• Test No. 26 This test illustrates the prior art and uses, during the milling step, 1.35% by weight, relative to the dry weight of mineral matter, of a polymer of the prior art which is obtained by conventional radical polymerization and which is composed, in percentage by weight, of 81.5% of methoxy polyethylene glycol methacrylate of molecular weight 2000, 4.9% of methacrylic acid, and 13.6% of acid. acrylic.
• This test differs from test No. 22 in that the grinding operation was stopped so as to obtain a dry extract equal to 72.9% by dry weight of mineral matter relative to the total dry weight of the suspension. .
• Test No. 27 This test illustrates the invention and implements 1.35% by weight, relative to the dry weight of mineral matter, of a polymer according to Test No. 7, during the milling step. .
• This test illustrates the invention and implements 1.35% by weight, based on the dry weight of mineral material, of a polymer according to test No. 8, during the grinding step.
• Reading Table 4 demonstrates that the characteristics of the aqueous suspensions according to the invention are similar to those of the suspensions according to the prior art, in terms of dry extract ES and particle size.
• the opacity in terms of measuring the diffusion coefficient of the light S, the dry films resulting from the drying of the coating sauces containing the suspension according to the invention is much better than in the case of the prior art.
• This example illustrates the use according to the invention of water-soluble polymers of controlled structure obtained by a controlled radical polymerization process implementing, as a polymerization initiator, a particular alkoxyamine of formula (A '), as well as the use according to the invention of aqueous dispersions containing said polymers and optionally a polymer according to the prior art, in a process for manufacturing dry products containing mineral materials, as agents improving the opacity and whiteness of said dry products.
• the method of manufacturing said dry products is characterized in that it comprises a step of grinding in water followed by a concentration step in water: the two stages take place using a polymer according to the prior art (case of the prior art), or with use of a polymer according to the invention (case of the invention), or with the use of a polymer according to the invention during the step of grinding and a polymer according to the prior art during the concentration step (case of the invention).
• the process leads to the production of an aqueous dispersion of mineral materials, which allows the manufacture of coating colors.
• the manufacturing process is also characterized in that it makes it possible to obtain dry coatings which are dry films resulting from the drying of said coating coatings which have previously been applied to papers.
• the percentage by weight of particles having a diameter of less than 1 ⁇ m and 2 ⁇ m, respectively denoted% ⁇ 1 ⁇ m and% ⁇ 2 ⁇ m, is determined using a Sedigraph TM 5100 device marketed by MICROMERITICS TM.
• the suspension obtained is then concentrated in the presence of a dispersant of the prior art or by use of a polymer according to the invention.
• a dispersion of mineral material is then obtained, the dry extract of which is noted as ES 2 (in dry weight of mineral matter relative to the total weight of the suspension) is measured, the particle size characteristics thereof as determined above remaining unchanged.
• the dispersion thus obtained is mixed with a styrene-acrylic binder marketed under the name Acronal TM S360D by the company BASF TM, in a proportion of 100 grams by dry weight of calcium carbonate, for 12 parts by weight. binder state.
• a polypropylene-based plastic paper marketed under the name Synteape TM by the company ARJO-WIGGINS TM is then coated by means of a laboratory coater of the type Hand Coater TM model KC202 and this, for obtain different layer weights between 5 and 50 g / m ".
• the samples are then dried for 10 minutes at 90 ° C.
• Finnfix TM 10 which is a carboxymethyl cellulose marketed by METSA SERLA TM;
• Mowiol TM 6.98 which is a polyvinyl alcohol marketed by CLARIANT TM;
• Blancophor TM P which is an optical brightener marketed by CIBA TM;
• the pH of the sauce is fixed at 8.5 by adding sodium hydroxide.
• pre-coated carrier papers having a basis weight of 76 g / m 2 are then coated by means of a Hand Coater TM model KC202 laboratory coater to obtain an equal layer weight. at 10 g / m 2 .
• the samples are then dried for 10 minutes in an oven at 90 ° C.
• Each sheet of coated paper is subjected to a luminous radiation of wavelength equal to 457 nm by means of an Elrepho TM 3000 spectrophotometer marketed by DATACOLOR TM on a black plate to determine the reflectance factor of the paper coated on a black background R 2 and on a stack of at least 10 sheets of coated paper to determine the reflectance factor R 3 of a thickness of opaque coated papers.
• Test No. 29 This test illustrates the prior art and uses, during the grinding step, 0.50% by dry weight, relative to the dry weight of mineral matter, of a polymer of the prior art which is obtained by conventional radical polymerization and which is composed, in percentage by weight, of 81.5% of methoxy polyethylene glycol methacrylate 2000 molecular weight, 4.9% methacrylic acid, and 13.6% acrylic acid, and 0.50% dry weight of the same polymer relative to the dry weight of mineral material during the concentration step .
• This test illustrates the invention and implements 0.50% by dry weight of the polymer according to test No. 6 with respect to the dry weight of mineral material, during the grinding stage, and 0.50% by dry weight. of the same polymer with respect to the dry weight of mineral material during the concentration step.
• This test illustrates the invention and implements 0.50% by dry weight of the polymer according to test No. 2 with respect to the dry weight of mineral material, during the grinding stage, and 0.70% by dry weight. relative to the dry weight of mineral matter, a polymer of the prior art which is obtained by conventional radical polymerization and which is composed, in percentage by weight, of 81.5% of methoxy polyethylene glycol methacrylate of molecular weight 2000 , 4.9% methacrylic acid, and 13.6% acrylic acid during the concentration step.
• This test illustrates the invention and implements 0.50% by dry weight of the polymer according to test No. 3 with respect to the dry weight of mineral material, during the grinding stage, and 0.50% by dry weight. of the same polymer with respect to the dry weight of mineral material during the concentration step.
• Table 5 demonstrates that the characteristics of the aqueous dispersions according to the invention are similar to those of the dispersion according to the prior art, in terms of solids content ES 2 and particle size distribution.
• This example illustrates the use according to the invention of water-soluble polymers of controlled structure obtained by a controlled radical polymerization process implementing, as a polymerization initiator, a particular alkoxyamine of formula (A '), as well as the use of the aqueous suspensions containing said polymers, in a process for producing dry products containing inorganic materials, as agents improving the opacity, brightness and whiteness of said products.
• the manufacturing process of said products is characterized in that it comprises a grinding step using a polymer according to the prior art or using a polymer according to the invention.
• the process thus leads to obtaining aqueous suspensions of mineral matter. Said suspensions then make it possible to manufacture papermaking coatings.
• the manufacturing method is also characterized in that it leads to the production of dry coatings which are dry films resulting from the drying of said coating coatings which have been previously applied to papers.
• the percentage by weight of particles having a diameter of less than 1 ⁇ m and 2 ⁇ m, respectively denoted% ⁇ l ⁇ m and% ⁇ 2 ⁇ m, is determined using a Sedigraph TM 5100 device marketed by MICROMERITICS TM.
• the dry extract ES expressed as a percentage by dry weight of mineral matter relative to the total dry weight of said suspension, is determined.
• the suspension thus obtained is mixed with a styrene-acrylic binder marketed under the name Acronal TM S360D by the company BASF TM, in a proportion of 100 grams by dry weight of calcium carbonate, for 12 parts by weight. binder state.
• a polypropylene-based plastic paper marketed under the name Synteape TM by the company ARJO-WIGGINS TM is then coated by means of a laboratory coater of the type Hand Coater TM model KC202 and this, for obtain different layer weights between 5 and 50 g / m.
• the samples are then dried for 10 minutes at 90 ° C. in an oven.
• a paper coating sauce containing: 68% by dry weight of mineral matter, based on the total weight of the coating color, introduced via the appropriate amount of the suspension of mineral material prepared previously;
• the coated paper is then calendered at 80 ° C. and under a pressure of 40 bars, using a calender machine of the RK 22 HU type marketed by DR DRAMISCH TM & CO.
• coated plastic papers as defined above: the value of the diffusion coefficient of the light before calendering and according to the method previously described, denoted S (m 2 / kg); as well as the value of the gloss 75 ° TAPPI after calendering and according to the method previously described, noted B] -75 ; for pre-coated, then coated and calendered paper as defined above:
• This test illustrates the prior art and uses, during the grinding step, 0.65% by dry weight, relative to the dry weight of mineral matter, of a polymer of the prior art which is a homopolymer of acrylic acid neutralized with a mixture of 30% by weight of calcium hydroxide and 70% by weight of sodium hydroxide (in molar equivalent).
• This test illustrates the invention and uses, during the milling step, 1.35% by dry weight, relative to the dry weight of mineral matter, of the polymer obtained in test No. 12.
• the value of the diffusion coefficient of the light before calendering denoted S (m 2 / kg), as well as the value of the gloss 75 ° TAPPI after calendering, denoted Bi 75 ; for the pre-coated and then coated backing papers as defined above, and
• Table 6 characteristics of aqueous suspensions of mineral matter and optical properties of dry coatings.
• Reading Table 6 demonstrates that the characteristics of the aqueous suspension according to the invention are similar to those of the suspension according to the prior art, in terms of dry extract ES and particle size.
• the opacity in terms of measuring the ratio R 2 / R 3 , their brightness, in terms of measuring the coefficient B 1 75 , and also their whiteness, in terms of measuring the WC I E coefficient, are better in the context of the invention.
• This example illustrates the use according to the invention of water-soluble polymers of controlled structure obtained by a controlled radical polymerization process employing, as a polymerization initiator, a particular alkoxyamine of formula (A '), in a process of manufacture of dry products containing mineral substances, as agents improving the gloss of said products.
• the process for manufacturing aqueous formulations of mineral materials is characterized in that said polymers are used as direct additives in the manufacture of aqueous paints, which allow, after drying, to obtain dry paint films.
• Mergal TM K6N is a bactericide sold by the company TROY TM Byk TM 34 is an antifoam agent marketed by the company BYK TM TiO2 RHD2 is a titanium dioxide powder sold by the company HUNTSMAN TM
• Neocryl TM XK 76 is an acrylic binder marketed by DSM TM
• Coatex TM Rheo 2000 TM is an associative acrylic thickener marketed by COATEX TM
• the formulations corresponding to tests Nos. 35, 36, 37 and 38 thus contain 0.2% by dry weight, relative to the total weight of the formulation, respectively Coatex TM BR3, R2006 / 001064
• Each paint was then applied by means of a standard manual film puller, to a thickness of 150 ⁇ m on a glass plate, and then dried for 72 hours under the standard conditions well known to those skilled in the art.
• Table 8 measurement of gloss at angles equal to 20 °, 60 ° and 85 ° (BS 20 , BS 6 O and BS 85 ) according to standard NF T 30-064.
• the direct use of the polymers according to the invention thus makes it possible to substantially improve the gloss of dry coatings which are dry films resulting from the drying of an aqueous paint formulation containing said polymers.
• This example illustrates the use according to the invention of water-soluble polymers of controlled structure obtained by a controlled radical polymerization process implementing, as a polymerization initiator, a particular alkoxyamine of formula (A '), as well as the use according to the invention of aqueous dispersions of mineral materials containing said polymers, in a manufacturing process of dry products containing mineral materials, as agents improving the gloss of said dry products.
• the method of manufacturing said dry products is characterized in that it comprises a step of grinding in water using said polymers, resulting in obtaining an aqueous suspension of mineral materials containing said polymers. Said suspension is then dried so as to obtain a dry powder of mineral material according to the invention. Said powder then allows the manufacture of plastics whose gloss is improved compared to plastics of the prior art.
• a calcium carbonate which is an Orgon calcite is initially milled in water in the presence of 0.70% by dry weight relative to the dry weight of calcium carbonate, of the polymer according to Test No. 12.
• a suspension of refined calcium carbonate the content by weight of which is equal to 60% by dry weight of calcium carbonate relative to the total weight of the suspension, and the percentages by weight of particles whose diameter is less than 1 ⁇ m and 2 ⁇ m, and measured using a Sedigraph TM 5100 device, are equal to 57.6% and 93.0%, respectively.
• the previously obtained suspension is then dried in a Niro TM MINOR MOBIL 2000 atomizer, applying the following parameters: inlet temperature equal to 350 ° C., outlet temperature of between 102 and 105 ° C., ventilation set at 99%, pressure of air equal to 4 bars.
• the mixing cycle in the Guédu mixer is as follows:
• the temperature of the extrusion device is set at 180 ° C. and the extrusion speed at 30 rpm. For each of the tests n ° 39 to n ° 41, the values of the motor torque, the pressure at the head of the screw and the flow rate were recorded.
• Table 9 values of the engine torque, screw head pressure and flow rate measured during extrusion of dry blends corresponding to tests No. 39, No. 40 and No. 41.
• any agglomerate is not observed during the tests. Moreover, for the tests corresponding to the invention, a very good dispersion of the filler within the polymer matrix is observed, which attests to a good compatibility of the dry powders according to the invention with the resin.
• the gloss measurements were carried out using a Micro-Tri-reflectance meter.
• Gloss TM marketed by BYK GARDNER TM under an exposure angle of 85 °.
• the direct use of the polymers according to the invention therefore makes it possible to improve the gloss of dry products which are plastics containing said polymers.
• Water-soluble polymers of controlled structure are thus obtained, whose monomeric composition as well as the molecular weight (measured according to the method previously described and expressed in g / mole) are given in tests No. 42 to 47.
• This GPC method also makes it possible to determine the polymolecularity index of this product which is equal to 2.0.
• This GPC method also makes it possible to determine the polymolecularity index of this product which is equal to 1.8.
• Test No. 46 This test leads to obtaining, from a controlled radical polymerization process using, as polymerization initiator Falcoxyamine of formula (A '), a water-soluble polymer having a composition by weight of, based on total mass of the monomers involved:
• This example illustrates the use according to the invention of water-soluble polymers of controlled structure obtained by a controlled radical polymerization process implementing, as a polymerization initiator, a particular alkoxyamine of formula (A '), as well as the use of the aqueous suspensions containing said polymers, in a process for manufacturing dry products containing mineral materials, as agents improving the opacity and brightness of said products.
• the manufacturing process of said products is characterized in that it comprises a grinding step using a polymer according to the prior art or using a polymer according to the invention.
• the process thus leads to obtaining aqueous suspensions of mineral matter. Said suspensions then make it possible to 6 001064
• the percentage by weight of particles having a diameter of less than 1 ⁇ m and 2 ⁇ m, respectively denoted% ⁇ l ⁇ m and% ⁇ 2 ⁇ m, is determined using a Sedigraph TM 5100 device marketed by MICROMERITICS TM.
• the solids content ES expressed as a percentage by dry weight of mineral matter relative to the total weight of said suspension, is then determined.
• the suspension thus obtained is mixed with a styrene-acrylic binder sold under the name Acronal TM S360D by BASF TM, in a proportion of 100 grams by dry weight of calcium carbonate for 12 hours. parts in the binder state.
• a polypropylene-based plastic paper marketed under the name Synteape TM by the company ARJO-WIGGIN S TM is then coated by means of a laboratory coater of the type Hand Coater TM model KC202 and this, to obtain different layer weights of between 5 and 50 g / m 2 .
• the samples are then dried for 10 minutes at 90 ° C. in an oven.
• the coated papers are then calendered at 90 ° C. and at a pressure of 60 bars, by means of a calendering apparatus of the RK 22 HU type marketed by DR DRAMISCH TM & CO.
• coated plastic papers as defined above: the value of the diffusion coefficient of the light before calendering and according to the method previously described, denoted S (m 2 / kg); - as well as the gloss value 75 ° TAPPI after calendering and according to the previously described method, denoted B 75 ;
• Test No. 48 illustrates the prior art and uses, during the grinding step, 0.65% by dry weight, relative to the dry weight of mineral matter, of a polymer of the prior art which is a homopolymer of acrylic acid neutralized with a mixture of 50% by weight of sodium hydroxide and 50% by weight of magnesium hydroxide (in molar equivalent).
• Tests Nos. 49 to 52 illustrate the invention and use during the milling step 1, 2% by dry weight, relative to the dry weight of mineral matter, of a polymer which is respectively the described polymer. in trials 43, 44, 45, 46.
• Table 11 characteristics of aqueous suspensions of mineral matter and optical properties of dry coatings (* not measured) Reading Table 11 demonstrates that the characteristics of the aqueous suspension according to the invention are similar to those of the suspension according to the prior art, in terms of dry extract ES and particle size.
• the Applicant wishes to point out that the aqueous suspensions of mineral substances obtained for tests Nos. 49 to 52 do not contain foam, unlike the suspension obtained for test No. 48.
• This is due to the fact that use of the butoxypolyoxypropylene hemimaleate monomer comprising 19 units of oxypropylene and the silane monomer of formula R - A - Si (OB) 3 where R denotes the methacrylate group, A denotes the propyl radical and B denotes the methyl radical, which have a anti-foam character.
• the manufacturing process is also characterized in that it leads to obtaining dry coatings which are dry films resulting from the drying of said paints which have been previously applied to glass plates.
• the suspension obtained has a solids content equal to 60%. This one is dried.
• a painting is then produced whose composition is as follows:
• Synolac TM 6868 WL 75 marketed by the company CRAY VALLEY TM
• Each paint (for Run 53 and Run 54) was then applied using a standard manual film puller, 150 ⁇ m thick on a glass plate, and then dried for 72 hours under standard conditions. well known to those skilled in the art.
• the gloss of the dry films obtained was measured on a Micro-Tri-Gloss TM reflectometer marketed by BYK GARDNER TM at an angle equal to 20 ° according to NF T 30-064.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Paper (AREA)
• Paints Or Removers (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Polymerisation Methods In General (AREA)

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• 2005
  • 2005-05-20 FR FR0505054A patent/FR2885906A1/fr not_active Withdrawn
• 2006
  • 2006-05-12 EP EP06764607A patent/EP1888657A2/de not_active Withdrawn
  • 2006-05-12 CA CA002608433A patent/CA2608433A1/fr not_active Abandoned
  • 2006-05-12 US US11/913,948 patent/US20080199419A1/en not_active Abandoned
  • 2006-05-12 TW TW095116869A patent/TW200712072A/zh unknown
  • 2006-05-12 WO PCT/FR2006/001064 patent/WO2006123038A2/fr not_active Application Discontinuation
  • 2006-05-15 AR ARP060101944A patent/AR055791A1/es not_active Application Discontinuation
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